CN104313663B - A kind of N, Ti3+The visible light catalytic TiO of codope2The preparation method of nano-tube array - Google Patents
A kind of N, Ti3+The visible light catalytic TiO of codope2The preparation method of nano-tube array Download PDFInfo
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Abstract
A kind of N, Ti3+The visible light catalytic TiO of codope2The preparation method of nano-tube array, belong to technical field of nano material, this method grows TiO in fluorine-containing electrolyte, using two electrode systems in titanium sheet2Nanotube, then by TiO2It is to obtain N doping TiO at 450~550 DEG C in being calcined in air atmosphere that nano-tube array, which is suspended on temperature above melamine,2Nanotube (N TiO2)；By array under negative potential, in inertia electrolyte constant potential polarization, obtain N, Ti3+The TiO of codoping modified visible ray PhotoelectrocatalytiPerformance Performance2Nano-array.The present invention successfully prepares Ti3+/ N doping vario-properties TiO2Nano-tube array, with TiO before modified2Nano-tube array is compared, modification TiO2The visible light-responded of nano-tube array significantly improves, and shows the ability that stronger visible ray removes persistent organic pollutants；Technique is simple, improves TiO2In the photoelectrocatalysis efficiency of visible ray, so that it can be used for the fields such as environmental improvement, opto-electronic conversion, catalyzing manufacturing of hydrogen.
Description
Technical field
The invention belongs to technical field of nano material, more particularly to a kind of visible light catalytic TiO2The preparation of nano-tube array
Method.
Background technology
At present, the quality of China's running water is also poor, and 2000 gas chromatographies have been detected in running water, including
Carcinogenic or suspicious carcinogenic material.Therefore, the new research and development for removing the organic matter technology in running water are by increasingly
Extensive concern.Due to TiO2Nano-tube array, which has, a variety of advantages such as easily reclaims, can reuse, and prepares ordered arrangement
TiO2Nano-tube array is TiO2One important development direction in nanotube preparation research field.But due to TiO2Forbidden band it is wider
(3.0~3.2eV), 4% or so using solar energy is only capable of, and light induced electron and the compound of hole cause photo-quantum efficiency very
It is low.How to TiO2It is modified, extends its light action scope to visible ray, the research for turning into numerous scholars in recent years is burnt
Point.Therefore, domestic and foreign scholars have carried out substantial amounts of research, the results showed that to TiO2It is a kind of effective modified hand to be doped
Section.At present, most successful doping method is by TiO2Powder is calcined in nitrogen and atmosphere of hydrogen and introduces nitrogen and Lacking oxygen
TiO2Lattice, by hydroxyl (- OH) introduce TiO2Surface.Although the method greatly improves TiO2Visible light photocatalysis
Can, but its requirement to extra raw material (hydrogen) and equipment is considered, still it is not a kind of economic method.
The content of the invention
It is an object of the invention to overcome above-mentioned deficiency, there is provided one kind improves TiO2The visible photoelectrocatalysis of nano-tube array
Performance, strengthen the modification TiO of its utilization ratio to visible ray2Nano-tube array (N, Ti3+Codope) preparation method.
The used to achieve the above object technical scheme of the present invention is：A kind of N, Ti3+The visible light catalytic of codope
TiO2The preparation method of nano-tube array, it is characterised in that：Comprise the following steps：
(1) TiO is prepared using two electrode systems2Nanotube：
Using titanium or titanium alloy as anode, platinized platinum is as negative electrode, additional 20~50V in the electrolyte of fluoride
Self assembly TiO is made in 0.5~4h of constant-potential electrolysis2Nano-tube array；
(2) N-TiO is prepared2:
By TiO2Nano-tube array is suspended on above melamine, and temperature is in being forged in air atmosphere at 450~550 DEG C
Burn, obtain N doping TiO2Nanotube, i.e. N-TiO2；
(3) cathodic reduction processing prepares auto-dope TiO2Nano-tube array：
By the N-TiO of the crystallization prepared by step (2)2Nano-tube array is under negative potential, stable state pole in inertia electrolyte
Change, obtain the N-TiO of auto-dope modification2Nano-tube array.
Further, in the step (1), contained fluoride be ammonium fluoride in electrolyte, its concentration for 0.1~
1.5mol/L。
Further, in the step (2), by TiO2Nano-tube array is suspended on the melamine that quality is 0.1~1g
Top.
Further, the step (3) is carried out in three-electrode system；Wherein, working electrode is prepared by step (2)
The N-TiO of crystallization2Nano-tube array, is platinized platinum to electrode, and reference electrode is saturated calomel electrode.
Further, in the step (3), inertia electrolyte is the salting liquid that concentration is 0.01~5mol/L.
Further, in the step (3), the steady-state polarization time is 5~60min.
Further, in the step (3), steady-state polarization voltage is -2~-1V.
Beneficial effects of the present invention are embodied in：
(1) present invention successfully prepares Ti3+/ N doping vario-properties TiO2Nano-tube array, with TiO before modified2Nanotube
Array is compared, the codoping modified TiO2The visible light-responded of nano-tube array significantly improves, and shows stronger visible ray and goes
Except the ability of persistent organic pollutants；
(2) it is of the invention from preparation TiO compared with traditional heat treating process2Nanotube adulterates TiO to N2Nanotube, overcome
Calcined under traditional nitrogen atmosphere, technique is simple, saves raw material and equipment；
(3) Ti of the present invention3+Doped portion is using electrochemical process to TiO2Nanotube is modified, by controlling electricity
The amount for the Lacking oxygen that the factor can controls such as pressure, electrolyte composition introduce.
Brief description of the drawings
Fig. 1-(a), Fig. 1-(b) are respectively prepared auto-dope high conductivity TiO2SEM figure (the scannings of nano-tube array
Electron microscope) and EDS spectrograms (energy spectrum diagram)；
Fig. 2 is TiO2、Ti3+-TiO2、N-TiO2And Ti3+/N-TiO2The photoelectricity flow graph of nanotube；
Fig. 3 is TiO2、Ti3+-TiO2、N-TiO2And Ti3+/N-TiO2Nanotube produces the comparison diagram of hydroxyl radical free radical；
Fig. 4 is TiO2And Ti3+/N-TiO2The comparison diagram of nanotube visible ray photoelectrochemical degradation phenol.
Embodiment
The present invention is described in detail with reference to specific embodiment, but the invention is not limited in specific embodiment.
Embodiment 1
(1) after pure titanium sheet is cleaned by ultrasonic with deionized water, it is 1 to immerse volume ratio:3:6 HF, HNO3、H2In O mixed liquors
1min is etched, is cleaned immediately with deionized water, is dried in nitrogen stream；Weigh 0.37g NH4It is 90ml second two that F, which is dissolved in volume,
In alcohol and the mixed liquor of 10ml deionized waters, NH is configured to4F concentration is 0.1mol/L electrolyte；Using the titanium sheet after processing as
Anode, platinized platinum are negative electrode, are depressed in 20V direct current of voltage regulation and carry out anodic oxidation reactionses 0.5h, after reaction terminates, use deionized water
Cleaning, dries, obtains amorphous TiO in atmosphere2Nano-tube array；
(2) by amorphous TiO2Nanotube is suspended on above 0.1g melamines, is put into 450 DEG C of calcining 2h in Muffle furnace,
Make its crystallization and prepare the TiO of N doping2, after testing, its SEM figures, EDS spectrograms are as shown in fig. 1；
(3) using platinized platinum as anode, the TiO of crystallization2Nanotube is negative electrode, 0.01mol/L Na2SO4Solution is electrolyte, outside
Add -1V DC voltages to be electrolysed 5min, obtain Ti3+The visible light-responded TiO being modified with N2Nano-tube array.
According to the Ti prepared to the embodiment3+The codoping modified TiO with N2Nano-tube array carries out interpretation of result：
1.SEM schemes and EDS spectrograms：Ti3+/N-TiO2The SEM of nano-tube array shows in cathodic reduction TiO before and after the processing2
Nano-tube array structure does not change.Its EDS shows that using the method for melamine suspension calcining N element success can be made
Be doped to TiO2In nanotube (as shown in fig. 1).
2. photoelectric properties：The test of its photoelectric current is carried out in 0.1mol/L sodium sulphate electrolyte.Working electrode
It is platinum electrode to electrode for photochemical catalyst electrode, calomel electrode is reference electrode, and applied voltage is that 0.6V light sources are fluorescent lamp.
Shown in Fig. 2, TiO2The photoelectric current of nanotube is only 27 μ A, is all significantly improved by its modified photoelectric current, wherein Ti3+/ N changes
Nanotube photoelectric current after property is up to 100 μ A.Show Ti3+With TiOs of the N after codoping modified2Nanotube photoresponse under visible light
It is obvious to become strong, the utilization ratio of visible ray is uprised.
3. the detection of hydroxyl free：The detection of hydroxyl radical free radical is using fluorimetry.With 1 × 10-3Mol/L is to benzene
The basic sulfate sodium solution (0.1mol/L) of dioctyl phthalate is electrolyte, and working electrode is photochemical catalyst electrode, is platinum electricity to electrode
Pole, calomel electrode are reference electrode, and applied voltage is that 0.6V light sources are fluorescent lamp.Shown in Fig. 3, Ti3+/N-TiO2Caused hydroxyl
Number of free radical is higher than other three kinds of electrode materials.This also illustrates Ti3+/N-TiO2The visible light photocatalysis effect of nanotube is more
It is good.
4. PhotoelectrocatalytiPerformance Performance：The power of its visible ray PhotoelectrocatalytiPerformance Performance is investigated by degradation of phenol.Its photoelectric current
Test be to be carried out in 0.1mol/L sodium sulphate electrolyte.Working electrode is photochemical catalyst electrode, is platinum electricity to electrode
Pole, calomel electrode are reference electrode, and applied voltage is that 0.6V light sources are fluorescent lamp.Shown in Fig. 4, after the 7h that degrades respectively, TiO2It is right
The degradation rate of phenol is only 26%, and Ti3+TiO modified/N2The degradation rate of Pyrogentisinic Acid is 74%.This shows Ti3+/N-TiO2
Nanotube in terms of the degraded of hardly degraded organic substance advantageously.
Pass through above-mentioned analysis, the Ti of the method preparation of the present embodiment3+The TiO that/N is modified2Nano-tube array is than being modified
Before show more preferable photoelectric properties, it is higher to the utilization rate of visible ray, more have in degraded persistent organic pollutants field excellent
Gesture.
Embodiment 2
(1) after pure titanium sheet is cleaned by ultrasonic with deionized water, it is 1 to immerse volume ratio:3:6 HF, HNO3、H2In O mixed liquors
1min is etched, is cleaned immediately with deionized water, is dried in nitrogen stream；Weigh 2.96g NH4It is 90ml second two that F, which is dissolved in volume,
In alcohol and the mixed liquor of 10ml deionized waters, NH is configured to4F concentration is 0.8mol/L electrolyte；Using the titanium sheet after processing as
Anode, platinized platinum are negative electrode, are depressed in 35V direct current of voltage regulation and carry out anodic oxidation reactionses 2h, clear with deionized water after reaction terminates
Wash, dry in atmosphere, obtain amorphous TiO2Nano-tube array；
(2) by amorphous TiO2Nanotube is suspended on above 0.7g melamines, is put into 500 DEG C of calcining 2h in Muffle furnace,
Make its crystallization and prepare the TiO of N doping2；
(3) using platinized platinum as anode, the TiO of crystallization2Nanotube is negative electrode, 2.5mol/L Na2SO4Solution is electrolyte, outside
Add -1.3V DC voltages to be electrolysed 10min, obtain Ti3+The visible light-responded TiO being modified with N2Nano-tube array.
Embodiment 3
(1) after pure titanium sheet is cleaned by ultrasonic with deionized water, it is 1 to immerse volume ratio:3:6 HF, HNO3、H2In O mixed liquors
1min is etched, is cleaned immediately with deionized water, is dried in nitrogen stream；Weigh 5.55g NH4It is 90ml second two that F, which is dissolved in volume,
In alcohol and the mixed liquor of 10ml deionized waters, NH is configured to4F concentration is 1.5mol/L electrolyte；Using the titanium sheet after processing as
Anode, platinized platinum are negative electrode, are depressed in 50V direct current of voltage regulation and carry out anodic oxidation reactionses 4h, clear with deionized water after reaction terminates
Wash, dry in atmosphere, obtain amorphous TiO2Nano-tube array；
(2) by amorphous TiO2Nanotube is suspended on above 1g melamines, is put into 550 DEG C of calcining 2h in Muffle furnace, is made
Its crystallization and the TiO for preparing N doping2；
(3) using platinized platinum as anode, the TiO of crystallization2Nanotube is negative electrode, 5mol/L Na2SO4Solution is electrolyte, additional-
2V DC voltages are electrolysed 60min, obtain Ti3+The visible light-responded TiO being modified with N2Nano-tube array.
Claims (5)
1. a kind of N, Ti3+The visible light catalytic TiO of codope2The preparation method of nano-tube array, it is characterised in that：Including following
Step：
(1) TiO is prepared using two electrode systems2Nanotube：
Using titanium or titanium alloy as anode, platinized platinum is as negative electrode, the permanent electricity of additional 20~50V in the electrolyte of fluoride
Self assembly TiO is made in 0.5~4h of piezoelectricity solution2Nano-tube array；
(2) N-TiO is prepared2:
By TiO2Nano-tube array is suspended on above the melamine that quality is 0.1~1g, and temperature is in air at 450~550 DEG C
Calcined in atmosphere, obtain N doping TiO2Nanotube, i.e. N-TiO2；
(3) cathodic reduction processing prepares auto-dope TiO2Nano-tube array：
By the N-TiO of the crystallization prepared by step (2)2Nano-tube array is under negative potential, steady-state polarization in inertia electrolyte, obtains
The N-TiO being modified to auto-dope2Nano-tube array, this step are carried out in three-electrode system；Wherein, working electrode is step
(2) N-TiO of the crystallization prepared by2Nano-tube array, is platinized platinum to electrode, and reference electrode is saturated calomel electrode.
2. a kind of N, Ti according to claim 13+The visible light catalytic TiO of codope2The preparation method of nano-tube array,
It is characterized in that：In the step (1), contained fluoride is ammonium fluoride in electrolyte, and its concentration is 0.1~1.5mol/L.
3. a kind of N, Ti according to claim 13+The visible light catalytic TiO of codope2The preparation method of nano-tube array,
It is characterized in that：In the step (3), inertia electrolyte is the salting liquid that concentration is 0.01~5mol/L.
4. a kind of N, Ti according to claim 13+The visible light catalytic TiO of codope2The preparation method of nano-tube array,
It is characterized in that：In the step (3), the steady-state polarization time is 5~60min.
5. a kind of N, Ti according to claim 13+The visible light catalytic TiO of codope2The preparation method of nano-tube array,
It is characterized in that：In the step (3), steady-state polarization voltage is -2~-1V.
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| CN106732492A (en) * | 2016-11-23 | 2017-05-31 | 天津城建大学 | S/Ti3+The preparation method of codope TiO2 nano-tube arrays |
| CN110280284B (en) * | 2019-06-09 | 2022-03-25 | 浙江理工大学 | Synchronous preparation of C3N4And TiOxN2-xMethod for visible light catalyst |
| CN111185148B (en) * | 2020-02-21 | 2022-09-02 | 大连理工大学 | Ce-Zn modified TiO 2 Preparation method and application of nanotube array composite catalytic material |
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